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Pyrolysis 72 (2004) 97–102
Pyrolysis of municipal plastic wastes for recovery of gasoline-range hydrocarbons
Department of Chemical Engineering, Selcuk University, Konya, Turkey Accepted 2 March 2004 Available online 18 May 2004
Abstract This paper describes non-catalytic pyrolysis of plastic waste materials. Three types of waste plastics were used in this study: polystyrene (PS), polyethylene (PE) and polypropylene (PP). Under pyrolysis conditions, plastic wastes can be decomposed into three fractions: gas, liquid and solid residue. The liquid products are usually composed of higher boiling point hydrocarbons. In order to obtain useful gasoline-range hydrocarbons from the pyrolytic oil, fractional distillation is preferred for product separation. More valuable chemical raw materials including benzene, toluene and other condensed aromatic hydrocarbons may be obtained by reﬁning the pyrolytic oil. The results showed that waste PS yielded higher liquid, and waste PE and PP yielded higher gaseous products. The dominant pyrolytic liquid product of PS waste was styrene. © 2004 Elsevier B.V. All rights reserved.
Keywords: Plastic waste; Plastic pyrolysis; Gasoline-range hydrocarbons; Re-reﬁning; Municipal
1. Introduction In recent years the consumption of plastics has increased drastically; as a consequence the responsible disposal of plastic wastes has created serious social and environmental arguments . Recycling and re-reﬁning are the applicable processes for upgrading of petroleum based plastic wastes (PBPWs) by converting them into reusable products such as gasoline and heavy oil. PBPW is a source of useful energy (fuels) and/or chemicals and has many advantages from an ecological point of view . Possible acceptable processes are cracking and pyrolysis. The cracking process yields a highly unstable low-grade fuel oil which can be acid-corrosive, tarry, and discolored along with a characteristically foul odor. The pyrolysis process consists of the thermal degradation of the wastes in the absence of oxygen/air. Plastics pyrolysis may provide for disposal of plastic wastes with recovery of valuable gasoline-range hydrocarbons. In pyrolysis, the polymeric materials are heated to high temperatures, so their macromolecular structures are broken down into smaller molecules and a wide range of hydrocarbons are
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formed. These pyrolytic products can be divided into a gas fraction, a liquid fraction consisting of parafﬁns, oleﬁns, naphthenes and aromatics, and solid residues. Pyrolysis appears to be a technique which is able to convert PBPWs into gasoline-range hydrocarbons . All human and industrial processes produce wastes, that is, normally unused and undesirable products of a speciﬁc process. Plastic wastes can be classiﬁed as industrial and municipal plastic wastes (MPWs) according to their origins; these groups have different qualities and properties and are subjected to different management strategies. The municipal solid waste (MSW) products include paper, containers, tin cans, plastics, aluminum cans, and food scraps, as well as sewage. MPWs normally remain a part of MSWs as they are discarded and collected as household wastes. Plastics usually account for about 7% of the total MSW by weight and much more by volume. In order to recycle MPWs, separation of plastics from other household wastes is required. The waste products of industry and commerce include plastic, paper, wood, and metal scraps, as well as agricultural waste products . Table 1 shows the contents of municipal solid waste. There are four major methods for conversion of organic wastes to synthetic fuels: (1) hydrogenation; (2) pyrolysis; (3) thermal and/or catalytic cracking, (4) gasiﬁcation: and (5) bioconversion [5,6].
0165-2370/$ – see front matter © 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jaap.2004.03.001
(3) thermocouple. Concern over the volumes being created has lead to a number of governments introducing new legislation for its recovery as a resource. while the liquid products contained mainly aromatic hydrocarbons.5 10. polyethylene (PE) and polypropylene (PP) wastes were collected from landﬁll in the form of cattery. (2) temperature transmitter.0 mm and o. At the highest pyrolysis temperature of 1008 K. Pyrolysis is a tertiary recycling process and has an ability to provide three end products: a gas. and (7) collection vessels for liquid products. Demirbas / J. The heating was carried out from 298 to 1025 K in nitrogen stream. 19.2 10.9 1.6 2.98 A. Plastic sample was weight for run 1.” 2. In order to assess the thermal behavior of the plastic samples.3 8. 17. alkene and alkane hydrocarbons and their branched chain derivatives. The pyrolysis experiments were carried out in a stainless steel tube with height 76.% of the pyrolysis product. Polyethylene was pyrolysed in a ﬁxed bed reactor and the pyrolysis gases passed to a secondary reactor containing Y-zeolite or zeolite ZSM-5 catalyst. The oil reservoir has ﬁltering capacities . the BTX-aromatics content is about 20 wt. At 911 K over 50 wt. The gaseous products contained a large C3 fraction. 963 and 1008 K in a technical-scale ﬂuidized bed reactor . The numerical simulations of the linear pyrolysis of cellulosic and polyethylene waste were investigated . The decomposition of a polymer mixture over HZSM-5 and orthophosphoric acid modiﬁed (PZSM-5) zeolite catalysts has been comparatively studied .0 1. The polyvinylchloride (PVC) waste was pyrolyzed at 911. and changed their composition with respect to the non-catalytic at the same pyrolysis temperature. The inﬂuence of zeolite catalytic upgrading of the pyrolysis gases derived from the pyrolysis of polyethylene has been investigated . (4) external heater. Isothermal conditions and a controlled heating program of 10 K/min were used.2 18. (5) steel reaction vessel. Polystyrene (PS).6 1. (6) ice baths. The Y-zeolite produced signiﬁcantly greater concentration of aromatic hydrocarbons in the derived oils compared to when zeolite ZSM-5 catalyst was used. Traditional recovery methods have generally concentrated on recycling of materials or incineration for energy . toluene and xylene (BTX).8 Literature reports several papers on pyrolysis of plastics [1. oil and a solid residue which all have the potential to be further utilized .2 Upper limit 50. The crude synthesis gas is injected into exhausted oil reservoirs. about the half of which consists of benzene.0 1. thermogravimetric analysis (TGA) and pyrolysis runs were carried out. Appl. The oils consisted of mainly aliphatic compounds represented by alkadiene. Netzch 429/409 thermal analyzer was used.d. They were shredded into 3 mm × 5 mm size. lowered the condensate. 1.4 mm. In this way atmospheric pollution is avoided. . Pyrolysis 72 (2004) 97–102 Table 1 Contents of municipal solid waste (wt.00 g and Fig. A schematic representation of the apparatus used is shown in Fig.8 2.% of an oil.2 2. For thermogravimetric analysis. (1) Digital balance. Simpliﬁed experimental device for plastic waste pyrolysis. the main product was highly aromatized oil. 1.8 7. Anal.d.7–16]. Catalytic decomposition increased the amount of gaseous products.8 0.3 7.7 21. Experimental Three types of waste plastics were used in this study.2 11. Plastic waste has become an increased problem in many industrialized countries.% of total) Component Paper waste Food waste Plastic matter Metal Glass Textile Wood Leather and rubber Miscellaneous Lower limit 33. The most common test method for cracking is described in ASTM D-1693 “Standard Test Method for Environmental Cracking of Ethylene Plastics. Plastics wastes are converted into synthesis gas. The experiment at 963 K yielded about 40 wt. The polyethylene was pyrolysed at 775 K.% of the pyrolysis product was oil with a boiling point less than 538 K.0 mm. i.
The products were analyzed mainly in liquid state using a Fisons Ins.18].A.0 42. Heat to tube was supplied from external heater and the power was adjusted to give an appropriate heat up time. .6 9. Conversion of plastic wastes into gasoline-range hydrocarbons via pyrolysis in the absence of a catalyst has been reviewed by Kaminsky [19. The simple thermocouple (NiCr–Constantan) was placed directly in the pyrolysis medium. The differences in TG curves could obviously be attributed to the macromolecular structure and pyrolysis mechanism. and the aromaticity degrees. PS thermal degradation is a radical chain process including initiation.4 – – 64. The thermogravimetric (TG) curves for PE. PP and PS wastes are depicted in Fig.8 24. The pyrolysis of PE and PP occurs through the random-chain scission mechanism and a whole spectrum of hydrocarbon products is obtained . The TG behaviors of PE and PP are similar. the heater was started at 298 K and terminated when the desired temperature. . Appl. While initial MW increases from 2200 to 50.9 52. and 0. Anal.6 0. Degradation ﬁnished between 720 and 760 K for the plastic wastes. For each run. which show that both of them have a constant degradation behavior at the involved temperature range.8 49. Table 2 shows the product Fig.20]. ZB-625 capillary column. The product distribution from PS pyrolysis depends on initial molecular weight (MW) of the PS sample . the chain defects of the polymers. Heating rate: 10 K/s. condensables as tarry liquids and wax degradation products and solid residue. Demirbas / J. The pyrolysis of PS occurs by both end-chain and random chain scission and the monomer recovery is only some 45% . Random-chain scission. transfer and termination steps .d.6 1.000 the yield of styrene increases from 67 to 78 wt. 2. The pyrolysis products were collected within three different groups as non-condensable gaseous products. Chain-stripping. but PS is different. gas chromatograph (model GC 8000) equipped with a ﬂame ionization detector.% of waste) Waste Pyrolysis temperature (K) 1033 1013 854 1023 Gas Oil Residue Other Polyethylene (PE) Polypropylene (PP) Polystyrene (PS) Mixture PE/PP/PS Source: Ref.25 i. Four types of mechanisms of plastics pyrolysis have been Different mechanisms are to some extent related to bond dissociation energies. 30 m long. PE thermal degradation consists of free radical formation and hydrogen abstraction steps .%. 55. Pyrolysis 72 (2004) 97–102 99 pyrolyzed in the tube.9 styrene – proposed : (1) (2) (3) (4) End-chain scission or depolymerization. The behavior of PE or PP and PS shows one main distinct weight loss step. Results and discussion PE and PP are the main components of MPWs.6 46. 3. Table 2 Product distribution in plastic pyrolysis (wt. as well as the presence of halogen and other hetero-atoms in the polymer chains . Cross-linking. TGA curves of PE. PP and PS wastes.4 48. Some chromatographic analysis of the gaseous products was also made.8 1. 2.6 1. Pyrolysis of plastics has been studied extensively in the past [17.
Heating rate: 10 K/s. The yield distributions of the pyrolytic products from municipal plastic waste are given in Fig. Individual yield of each gas product with increasing pyrolysis temperature is irregular.%.5 wt.3 to 42. distribution in plastic pyrolysis . Curves for yield distributions of pyrolytic products from municipal solid waste.4 wt. 5. Fig. 4 shows the yields of the gaseous products from pyrolysis of municipal solid waste. 3.100 A. From Table 3.6% with increasing pyrolysis temperature from 650 to 875 K. 4. the yields of gaseous products increase with increasing pyrolysis temperature. the yields of styrene increase from 56 to 64% with increasing pyrolysis temperature from 650 to 750 K and then decrease from 64 to 49. the yields of gaseous products increase from 12. 3.% with increasing pyrolysis temperature from 550 to 900 K. Pyrolysis 72 (2004) 97–102 Fig. . The yield distributions of the pyrolytic products from municipal solid waste are given in Fig. The yields of liquid products increase with increasing pyrolysis temperature up to 675 K and then slightly decrease from 675 to 850 K. While pyrolysis temperature increases from 650 to 875 K the yield of C2 –C4 hydrocarbons increases from 3. 5. The yields of liquid products increase with increasing pyrolysis temperature up to 750 K and then slightly decrease with temperature increasing from 750 to 900 K. The residual products from plastic pyrolysis are very low.8 to 22. As seen from Fig. 3. Curves for yields of the gaseous products from pyrolysis of municipal solid waste. Demirbas / J. Fig. The yield distributions of the pyrolytic products obtained from PS at different temperatures are shown in Table 3. Appl. From Fig. Anal.
8 6.2 5. Relationships between temperature and the yields of total-parafﬁn and naphthene are irregular. whereas oleﬁns and n-parafﬁns are less desired.8 17. Adequate volatility is required for smooth operation of petrol engines.5 1.2 10.6 6.5 1. Table 6 Yields of the products obtained by municipal plastic waste pyrolysis at different temperatures (K) Fraction Total-parafﬁn Total-oleﬁn Naphthene Aromatics Others 675 32.1 22.6 42.6 800 58.6 0.2 7.6 5.5 725 61.2 3.5 7.7 3. Table 6 shows the yield distributions of the pyrolytic products obtained from municipal plastic waste at different temperatures.8 0.6 1. Light hydrocarbons (LHs) have higher volatilities than those of heavy hydrocarbons (HHc).5 2.4 2.3 20.2 5.8 4.0 5.9 800 31.7 7.% with increasing temperature to 875 K.4 to 10.0 12. while pyrolysis temperature increases from 675 to 875 K the yield of total-parafﬁn fraction increases from 35.6 22.5 10.A.8 21.6 wt. From Table 4.9 18.7 1.8 1. The total yields of parafﬁns and oleﬁns of PE and PP wastes obtained by pyrolysis are higher than that of PS. naphthenes and isoalkanes are highly desirable.2 13.3 8.8 101 875 49.5 4.6 to 44.3 4. hydrocarbons from plastic pyrolysis are not suitable for gasoline usage.7 21.4 44.4 8. LHs may cause vapor lock when the engine is hot.4 19. While pyrolysis temperature increases from 675 to 875 K the yield of aromatics fraction increases from 1.2 1.%.1 800 43.6 21.%.5 1.6 wt.8 5.4 725 39.5 6.9 1.3 700 59.5 24.3 to 31.1 6.6 wt.5 37.0 7. Gasoline qualities are usually measured in terms of volatility and octane number of the hydrocarbons. While pyrolysis temperature increases from 675 to 725 K the yield of aromatics fraction increases from 7.0 6.%.2 31.2 increases from 675 to 875 K the yield of total-oleﬁn fraction decreases from 37.7 11. Anal.6 wt.6 750 64. Table 5 shows the yield distributions of the pyrolytic products obtained from PP at different temperatures.6 22. As seen from Table 6.5 23.7 to 35.4 5.6 875 29.5 13.6 3.2 6.%.4 800 24.%. Suitable hydrocarbons are in the C5 –C8 range.0 3. aromatics.% and then it decreases to 11. oleﬁns and aromatics.8 6. Heating rate: 10 K/s.5 9. The pyrolysis of plastic wastes produces a whole spectrum of hydrocarbons including parafﬁns.6 19. For gasoline production.5 6.2 42.9 to 13. HHs may not be volatile enough to start the engine when the engine is cold. The yield distributions of the pyrolytic products obtained from PE at different temperatures are shown in Table 4. 5.8 10.6 to 32. Curves for yield distributions of pyrolytic products from municipal plastic waste.9 15.2 wt.6 17. However. While pyrolysis temperature increases from 675 to 875 K the yield of total-oleﬁn fraction decreases from 42.8 38.4 875 44.6 35.6 2.1 875 33.8 7. From Table 5.1 32.5 0.7 34.0 725 28. while pyrolysis temperature increases from 675 to 875 K the yield of total-oleﬁn fraction decreases from 44.6 725 31.9 39.8 4.3 23.3 675 58. Pyrolysis 72 (2004) 97–102 Table 3 Yields of the products obtained by PS pyrolysis at different temperatures (K) Compound Styrene C2 –C4 hydrocarbons C5 –C8 hydrocarbons Methane Toluene Benzene 650 56.4 7. Appl.9 . Demirbas / J. Octane number a measure of the gasoline quality for prevention of early ignition which leads to cylinder knocks.4 7. Higher octane numbers are preferred in internal combustion engines.6 17.6 Table 5 Yields of the products obtained by PP pyrolysis at different temperatures (K) Fraction Total-parafﬁn Total-oleﬁn Naphthene Aromatics Others 675 30. while pyrolysis temperature Table 4 Yields of the products obtained by PE pyrolysis at different temperatures (K) Fraction Total-parafﬁn Total-oleﬁn Naphthene Aromatics Others 675 35.1 3.5 wt.2 wt.4 33.2 32.2 Fig.
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